Graft copolymer of ethylenically unsaturated carboxylic acids onto a substrate of poly-n-vinyl lactams

ABSTRACT

A graft copolymer of a monomer including at least one monomeric unsaturated aliphatic carboxylic acid and at least one additional monomer selected from the group consisting of aliphatic conjugated dienes and monoalkenyl aromatic compounds polymerized on a polymeric N-vinyl lactam substrate, stable aqueous emulsions containing same, and methods for producing such emulsions and graft copolymers useful as adhesives and other purposes.

United States Patent 11 1 Peterson et al.

[ GRAFT COPOLYMER OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS ONTO ASUBSTRATE OF POLY-N-VINYL LACTAMS [75] Inventors: William R. Peterson;Walter N.

Johnson, both of Chattanooga, Tenn.

[73] Assignee: GAF Corporation, New York, N.Y.

[22] Filed: June 15, 1973 [21} Appl. No.: 370,421

Related U.S. Application Data [62] Division of Ser. No. 171,006, Aug.11, 1971,

abandoned.

[52] U.S. Cl 260/879, 260/29.6 RW,

260/29.6 WB. 260/29.7 UP, 260/875, 260/880 R, 260/886 [51] Int. Cl. C08f15/00 [58] Field of Search 260/875, 879, 886

I 56] References Cited UNITED STATES PATENTS 3,301,808 l/l967 Mack260/886 1 1 Mar. 11, 1975 3,417,054 12/1968 Mcrijan et al. 260/8863,491,039 l/1970 Takahashi 260/886 3,635,868 l/1972 Barabas et a1.260/886 3,644,584 2/1972 Fryd 2(10/875 Primary Examiner-Paul LiebermanAttorney, Agent, or Firm-W. C. Kehm; Samson B. Leavitt; James N.Blauvelt [57] ABSTRACT A graft copolymer of a monomer including at leastone monomeric unsaturated aliphatic carboxylic acid and at least oneadditional monomer selected from the group consisting of aliphaticconjugated dienes and monoalkenyl aromatic compounds polymerized on apolymeric N-vinyl lactam substrate, stable aqueous emulsions containingsame, and methods for producing such emulsions and graft copolymersuseful as adhesives and other purposes.

6 Claims, No Drawings This is a continuation division of applicationSer. No. 171,006, filed Aug. 11, 1971 now abandoned.

BACKGROUND OF THE INVENTION This invention relates to novel graftcopolymers of a monomeric mixtureincluding at least one unsaturatedaliphatic carboxylic acid and at least one other monomer selected fromthe group consisting of aliphatic conjugated dienes and .monoalkenylaromatic compounds polymerized on a polymeric N-vinyl lactam substrateand a process for their production and to stable aqueous emulsionscontaining such graft copolymers and the process for producing suchemulsions.

It is well known that N-vinyl lactam monomers can be polymerized withother monomers but it has not been possible to successfully producecopolymers of the above monomeric mixture with N-vinyl lactams.

Attempts to prepare such a copolymer have heretofore lead to theformation of a copolymer containing very little N-vinyl lactam. If thecopolymerization is carried out in an aqueous system it will generallyyield mixtures of water soluble and insoluble copolymers, or mixtures ofhomopolymers and their unstable emulsions. Apparently, the monomericN-vinyl lactam would not cooperate to any appreciable extent.

SUMMARY OF THE INVENTION It is an object of the present invention toprovide a novel graft copolymer which is not subject to one or moredrawbacks of the prior art.

It is another object of the present invention to provide a stableaqueous emulsion containing the graft copolymer of the invention whichemulsion is not subject to one or more drawbacks of the prior art.

It is still another object of the present invention to provide a processfor making both the novel stable aqueous emulsion and recovering thenovel graft copolymer therefrom.

It is yet a further object of the present invention to provide for theproduction of the foregoing with existing facilities and thereforerepresents no additional capital expenditure.

Further objects and advantages of the invention will be set forth in thefollowing specification and in fact, will be obvious therefrom withoutbeing specifically referred to.

It has now been found that polymeric N-vinyl lactamwill successfullyfunction as a substrate in the production of carboxylated open chainaliphatic conjugated diene-monoalkenyl aromatic interpolymers as well asadding to the stability of the aqueous emulsion.

The attainment of the above objects is thus made possible by the presentinvention which includes the provision of a stable aqueous emulsioncontaining a graft copolymer of a monomer mixture including at least onemonomeric unsaturated aliphatic carboxylic acid and at least one monomerselected from the group consisting of aliphatic conjugated dienes andmonoalkenyl aromatic compounds polymerized on a polymeric N-vinyl lactamsubstrate.

The stable aqueous emulsions of this mention have surprisingly improvedproperties with respect to stability, low viscosity, film clarity, andthe like. Extraction,

solubility, and film clarity tests indicate that in these emulsions, thegraft polymeric product is in a high degree of interpolymerization orcopolymerization and contains a minimum amount of homopolymer or freepolymeric N-vinyl lactam. The resulting emulsions and graft copolymerstherein can be compounded with a 1 wide variety of additives such assalts, pigments, protective colloids, wetting agents, plasticizers,resins, waxes and the like to obtain a wide range of products for use inall fields in which polymeric emulsions are now used as in the paint,coatings, adhesives, polishes, textile and rubber fields. They haveparticularly good properties for use as tire cord adhesive in laminatingtire cord to rubber. In particular, the lamination of nylon tire cord torubber is a difficult lamination and the novel interpolymer of thisinvention has outstanding properties as an adhesive base for thislamination.

N-vinyl lactams and water soluble polymers thereof, and methods fortheir production are well known in the art. Thus, for example, US. Pat.No..2,3l7,804 discloses a suitable method for preparing N-vinyl lactamsand US. Pat. Nos. 2,215,450, 2,335,454 and 3,352,808 disclose methodsfor preparing water soluble polymers thereof and aqueous solutions,containing the same. As examples of N-vinyl lactams which may beemployed in producing in a known manner the operative aqueous solutionsof water soluble homopolymers thereof, there may be mentioned theN-vinyl derivatives of gamma-, delta-, and epsilon-lactams (N-vinylderivatives of the cyclic amides of gamma-, delta-, and epsilonaminocarboxylic acids of the aliphatic series), and lower alkyl (methyl,ethyl) substituted derivatives of such N-vinyl lactams. Among thisgroup, N-vinyl-Z-pyrrolidone (otherwise referred to asl-vinyl-Z-pyrrolidone, N-vinyl-a-pyrrolidone) is preferred. Asillustrative of other N-vinyl lactams within this group there may bementioned N-vinyl-Z-piperidone, N-vinyl-6- caprolactam,N-vinyl-5-methyl-2-pyrrolidone, N-vinyl- 3,3-dimethyl-2-pyrrolidone andthe like. Other N-vinyl lactams which may be employed includeN'vinyl-hexahydrophthalamidine, N-vinyl-naphthostyrile, etc. Dependingupon the extent of polymerization these polymeric N-vinyl lactams mayhave molecular weights ranging from at least 400 up to 2,000,000 ormore. The Fikentscher K value as described for example, in Schildknecht,Vinyl and Related Polymers, John Wiley & Sons, Inc., N.Y., 1952 (page676) is a convenient designation of relative degrees of polymerizationor relative molecular weights. Generally, there may be employed thosepolymeric N-vinyl lactams having a K value of about 5 to and preferablyabout 15 to 30, and mixtures thereof.

The polymerization catalysts such as a free radical supplying redoxcatalyst, useful in the present process are well known in the art. Mostof these catalysts are compounds yielding oxygen under the conditions ofpolymerization, as represented by the inorganic and organic peroxygen orperoxide compounds. As examples of such compounds, there may bementioned hydrogen peroxide, metal and alkali metal peroxides such as sodium, potassium, barium and zinc peroxide, diacyl peroxides such asdiacetyl, dibenzoyl and dilauroyl peroxide, dialkyl peroxides such asdi-tertiary-butyl peroxide and cyclohexene peroxide, hydroperoxides suchas tertiary-butyl hydroperoxide and p-methane hydroperoxide, peroxygenacids such as performic, persulfuric and peracetic acid and theirammonium, sodium and potassium salts, in addition to systems such aspotassium or ammonium persulfate-sodium bisulfite and the like. Otheroxygen-yielding compounds or sources include atmospheric oxygen, ozoneand the like.

Azo type catalysts, i.e., compounds containing the azo linkage, may alsobe employed. As example of such catalysts there may be mentioneda,a'-azobis-(a,'ydimethyl-valeronitrile),a,a'-azobis-(a-methylbutyronitrile),a,a'-azobis-(a-ethylbutyronitrile),a,a'-azodiisobutyramide, dimethyl anddiethyl,0z,aazodiisobutyrate, and the like.

The preferred catalysts effective for the production of optimum resultswith respect to a minimum of homo polymer and maximum emulsion stabilityand film clarity are the water soluble organic and inorganic peroxygencompounds referred to above, which are preferably employed along with anactivator. Some typical activators are amines, meta-bisulfites, ascorbicacid, Fe salts and other activators which are well known to thoseskilled in the art.

By the term monoalkenyl aromatic monomer it is intended to include thosemonomers wherein an alkenyl group is attached directly to an aromaticnucleus containing from about 6 to about 10 carbon atoms. Those monomersmay include alkyl, alkoxy and/or halo substituted compounds. Typical ofthese monomers are styrene, p-methyl styrene, o-methyl styrene,0-pdimethyl styrene, o-p-diethyl styrene, p-chlorostyrene, isopropylstyrene, tert-butyl styrene, o-methyl-pisopropyl styrene, aand Bbromovinyl benzene, aand ,8 chlorovinyl benzene, o-m or p-methoxybenzenes, and o-p-dichlorostyrene and the like and any mixtures thereof.The term is also intended to include vinyl naphthalenes, whichnaphthalenes may be used alone or mixtures thereof or in combinationwith the styrene monomers or mixture of styrenes. Because of itsavailability and ability to produce desirable polymers and for otherreasons, it is preferred to use styrene as the monoalkenyl aromaticmonomer.

By the term open chain aliphatic conjugated diene it is meant to includetypically, butadiene-l,3; 2- methyl-l,3-butadiene-(isoprene);2,3-dimethyl butadiene-1,3; piperylene; 2-neopentylbutadiene-l,3 andother hydrogen homologs of butadiene-l ,3 and in addition, thesubstituted dienes, such as 2-chloro-l,3- butadiene (chloroprene);2-cyano-butadiene-l,3 the substituted straight chain conjugatedpentadienes, the straight-and-branch-chain hexadienes, and the like andany mixtures thereof. The butadiene-l ,3 hydrocarbons, because of theirability to produce particularly desirable polymeric materials, arepreferred comonomers for use with the monoalkenyl aromatic monomer. Theethylene unsaturation in the above copolymerizable monomers ispreferably alpha, betaunsaturation, though it need not be.

The unsaturated aliphatic carboxylic acids, such as, but not limited to,monoethylenically unsaturated aliphatic monocarboxylic acids, includeany of those copolymerizable with the aforementioned monomers.Combination of two or more such acids are equally operable in thisinvention. The carboxylic acid may be added in its, free acid form or ina partially neutralized form, or may be converted, at least in part, toa salt while in an aqueous dispersion. Exemplary ethylenicallyunsaturated aliphatic monocarboxylic acids, include crotonic acid, a-chloro-crotonic acid, isocrotonic, cis-2-butenoic acid, hydrosorbicacid, acrylic acid, a -chloroacrylic acid, methacrylic acid, ethacrylicacid, vinylthiophenic acid, vinyl-furyacrylic acid, vinyl furoic acid, a-methyl sorbic acid, a -ethyl sorbic acid, a-chloro sorbic acid, a-bromo-sorbic acid, B -chloro sorbic acid, a- B-gamma-epsilon-dimethylsorbic acid, a -and- ,B-vinyl acrylic acids and the like.

There may also be used one or more ethylenically unsaturatedpolycarboxylic acids containing an activated olefinic double bond whichreadily functions in an addition polymerization reaction because it ispresent in the monomer molecule either in the a -Bposition with respectto a strongly polar or functional group, such as carboxyl or otherswhich are well known as activating groups or because it is adjacent to aterminal methylene group,

In general, the typically suitable polycarboxylic acids may berepresented by the following formula:

in whichR is preferably hydrogen or carboxyl, but may be carboxylicester, alkyl or alkenyl, Y is hydrogen, carboxyl, halogen, cyano, sulfo,alkyl, aryl, thienyl, or furyl, Z is methylene or a substitutedmethylene group or an ally], arylene, thienylene or furylene divalentradical, X is zero or any whole number, suitable not exceeding 3, and inwhich at least one of the groups R and Y is carboxyl-containing.

For example, such ethylenically unsaturated polycarboxylic acids includefumaric, maleic, citraconic, mesaconic, itaconic, teraconic, aconitic,ethyl maleic acid, methyl itaconic, muconic, hydromuconic, glutaconic,3-carboxypentadiene-(2,4)-oic-l, ,B-(pcarboxyphenyl) acrylic,2,4-pentadiendioic-l ,3 acid, the dimer and trimer of methacrylic acidand other monolefinic and polyolefinic polycarboxylic acids. Theutilization of these copolymerizable polybasic acids or their anhydrideswhich are readily hydrolyzed in the acidic polymerization provides ameans for direct introduction ofthe polycarboxylic acid groups into thepolymer chain.

It is to be understood that the polymerization heretofore described isconducted under such conditions that the monomeric components areindividually or in any combinations thereof graft polymerized as sidechains on the polymeric N-vinyl lactam substrate, without anysubstantial concurrent homopolymerization of such monomeric components.

If the polymerization reaction is allowed to proceed to approximatelypercent completion, then the ratios of the monomers charged representsthe ratio of the polymerized constituents in the polymer chain. Byacidic copolymer is meant a copolymer containing carboxyl groups on thepolymer chain.

The composition of the carboxylated graft copolym er can be varied by:

l. Varying ratio of polymeric N-vinyl lactam to the ratio of respectivemonomers;

2. Using different combinations of the different types of monomers;

3. Varying the ratio of the different types of monomers;

4. Using different monomers of the same type;

5. Varying the amounts of the same type of monomers; and

6. By combining l to 5 of the above.

The emulsions produced in accordance with this invention arecharacterized by unusually good stability, low to medium Viscosities atlow pH,'generally below about 2,500 cps (centiposes, BrookfieldViscosimeter), the ability to deposit a clear transparent film on aglass plate, and a graft copolymer product which is substantiallyinsoluble in water and in most hydrocarbon solvents, though it willswell in the latter.

If desired, the graft copolymer may be separated from the stable aqueousemulsion, notwithstanding the desirable properties of the emulsion as alatex. The separation may be accomplished by drying, i.e., air, spray orflash drying, or stripping or other generally accepted procedures knownin the art. The viscosity of the latex is largely dependent on theamount of polymeric N- vinyl lactam present, the initial molecularweight of said lactam and the pH.

It will be understood that in carrying out the process of thisinvention, known surface active agents, protective colloids,plasticizers, thickeners, chain transfer agents and other additives maybe added prior to, during or after the polymerization reaction iscompleted. Anionic or nonionic emulsifying agents may be employedalthough a mixture of anionic and nonionic agents is preferred. Asexamples of nonionic agents which may be employed, there may bementioned the condensation products of a plurality of moles of ethyleneoxide with organic compounds containing at least 8 carbon atoms and areactive hydrogen atom such as the water insoluble carboxylic andsulfonic acids, alcohols, thiols, phenols, hydroxy carboxylic acids,carboxy and sulfonic acids and amides, primary and secondary amines,hydroxyalkylamines, as disclosed, for example, in U.S. Pat. Nos.1,970,578, 2,205,021, 2,085,706, 2,002,613, 2,266,141, 2,677,700,2,213,477, 2,593,112, 2,454,542-545, and 2,174,761. As specific examplesof such nonionic agents there may be mentioned the reaction products of1 mole of nonylphenol with 9 to 100 E0. (moles ethylene oxide), 1 moleof castor oil with 20 E.O., 1 mole tall oil with 18 E.O., 1 mole ofoleyl alcohol with 20 E.O., 1 mole of dodecyl mercaptan with 9E.O., 1mole of soybean oil amine with 10 E.O., 1 mole of rosin amine with 32E.O., 1 mole of cocoanut fatty acid amine with 7 E.O., 1 mole of dinonylphenol with E.O., 1 mole of 0x0 tridecyl alcohol with 12 E.O., PluronicL62 and the like.

Suitable anionic surface active agents include the sulfonic acids,sulfate esters, and phosphate esters (particularly the primary andsecondary phosphate esters and mixtures thereof of the above mentionednonionic surface active agents as disclosed, for example, in U.S. Pat.Nos. 3,004,056 and 3,004,057and salts and mixtures thereof. Other suchanionic surface active agents include alkylaryl sulfonic acids such asdodecylbenzene sulfonic acid, alkyl sulfates such as laurylsulfate,sodium N-methyl taurides of higher (C to C fatty acids as disclosed, forexample, in U.S. Pat. Nos. 1,932,180, 3,013,035, 3,013,036 and3,057,889, isethionates such as sodium N-methyl isethionates esters ofhigher (C m to C fatty acids as disclosed, for example, in U.S. Pat.Nos. 2,923,724 and 3,004,049.

Protective colloids and/or thickening agents may also be employed ifdesired such as polyvinyl alcohol, copolymers such as the copolymer ofvinyl methyl ether and maleic anhydride, hydroxyethyl cellulose,carboxymethyl cellulose, natural gums and colloidal materials and thelike. Viscosities of up to 80,000 cps or more may thereby be obtainedwhen required.

A DETAILED DESCRIPTION OF THE INVENTION- For a fuller understanding ofthe nature and objects of the invention, reference should be had to thefollowing detailed description, taken in connection with the followingexamples, which are not to be considered as limiting, but ratherillustrative of the present invention. All parts and proportionsreferred to herein and in the appended claims are by weight unlessotherwise indicated.

In carrying out the polymerization reaction, the emulsifying agent,catalyst, charge water, unsaturated aliphatic carboxylic acid andpolymeric N-vinyl lactam are preferably admixed in any order inincrements or otherwise, with the remaining monomer mixture referred toabove. For better temperature control and production of a product withoptimum properties it is, however, preferred to add said remainingmonomer mixture gradually and/or in increments to the aqueous solutionof polymeric N-vinyl lactam and remaining components. It is preferred tocarry out the reaction at a temperature range of about 45C to about105C, preferably about 65C to about C, and under sufficient pressure tomaintain the conjugated diene liquid. The pH of the medium issubstantially non-critical, though a pH of below 7 and preferablybetween 2 and 6 is preferred. Completion of the reaction is determinedby cessation of evolution of heat and/or spot analysis for solidscontent and the like.

The polymerization reaction is substantially quantitative in that astable aqueous emulsion is produced containing a graft copolymer of thecarboxylated conjugated diene-monoalkenyl aromatic monomers graftpolymerized on the polymeric N-vinyl lactam substrate in the dispersedphase, with little or no polymeric product dissolved in the continuousaqueous phase.

The weight ratio of polymeric N-vinyl lactam to the total monomericmixture can be varied from about 1:99 to about 20:80 and the weightratio of monoalkenyl aromatic monomer, when employed, to conjugateddiene can vary from about 5:95 to about 75:25, the preferred range beingabout 25:75 to about 75:25. This unsaturated aliphatic carboxylic acidcan be employed in proportions of about .5 to about 20 parts andpreferably about 2 to about 6 parts by weight per parts of totalmonomeric mixture. The amount of catalyst should preferably be about0.05 percent to about 5.0 percent by weight based on the monomericmixture.

Some typical catalysts are persulfate salts, peroxides, hydroperoxideand other peroxy compounds. The polymerization reaction may be carriedout at 20-55 percent solids content, though it is preferred to conductsame at 38-46 percent solids. The emulsion can be further concentratedto 96 percent, if desired, after the polymerization, in accordance withstandard techniques.

EXAMPLE I To a 2 liter, stirred autoclave there is added: 675 gramsdistilled water 23 grams of 70 percent monylphenoxy poly(ethylene 7 7.5grams 1.0 parts) acrylic acid 7.5 grams (1.0 parts) methacrylic acid 60grams (8.0 parts) polyvinyl pyrrolidone (PVP) (K value=30) The reactoris turned on and thereafter a mixture of 418 grams (58 parts) styreneand 288 grams (40 parts) butadiene are added.

The reactor is heated to 75C for 18 hours, and the product is cooled anddischarged. The percent solids is 50.5 percent indicating substantiallycomplete conversion of monomer to polymer. The polymeric latex emulsionis stable. After being neutralized to a pH of 7.0 using ammonia, castonto a glass palte and cured for 12 minutes at 135C, a clear, waterinsoluble film with improved adhesion and tensile strength is obtained.

EXAMPLE II The procedure of Example I is repeated, except that the PVPof Example I is replaced by 60 grams (8 parts) of PVP having a K valueof 14. The same good results are obtained.

EXAMPLE III The procedure of Example I is repeated, except that 120grams (16 parts) of the same PVP is used. The same good results areobtained.

EXAMPLE IV The procedure of Example I is repeated, except that 45 grams(6 parts) of PVP having a K value of 60 is used instead of the 60 gramsof K value=30 material. The same good results are obtained.

EXAMPLE V The procedure of Example I is repeated, except that 30 grams(4 parts) of PVP having a K value of 90 is used. Similar results areobtained.

EXAMPLE VI The procedure of Example I is repeated, except that the PVPis post-added to a finished latex produced from the remaining materialsinstead of being charged initially. The properties of the resultinglatex are inferior as shown in the following table.

EXAMPLE VII The procedure of Example I is repeated, except that thetheoretical polymeric latex solids content is lowered to 40 percent byincreasing the amount of charge water, and the individual monomers, PVPK-30 and their amounts varied as shown in the following Table B.

TABLE B PARTS Mixed Acrylic Chloro- Buta- Acid & Meth- PVP- lsopreneprene Styrene diene acrylic Acid K-30 0 0 48 50 2 6 0 48 0 5O 2 6 48 0 050 2 6 O 50 48 0 2 6 50 0 48 0 2 6 0 O 28 2 6 0 70 28 0 2 6 7O 0 28 O 26 0 28 0 70 2 6 28 0 0 70 2 6 0 0 0 98 2 6 0 98 0 0 2 6 98 0 O 0 2 6 0 O67 3] 2 6 O 31 67 0 2 6 31 0 67 0 2 6 O 67 0 31 2 6 67 0 0 31 2 6 0 O 232 6 0 23 75 0 2 6 23 0 75 0 2 6 O 75 O 23 2 6 75 0 0 23 2 6 0 0 48 5O 28 O 48 0 50 2 8 48 0 0 50 2 8 0 50 48 0 2 8 50 0 48 O 2 8 O O 48 50 2 l20 48 0 50 2 I2 48 0 0 50 2 l2 0 50 48 O 2 I2 50 0 48 0 2 l2 0 0 48 50 2l6 0 48 O 50 2 16 48 0 0 50 2 l6 0 50 48 0 2 I6 50 0 48 0 2 l6 0 0 48 5O2 I8 0 48 O 50 2 I8 48 O O 50 2 l8 0 50 48 0 2 18 50 0 48 O 2 18 In allcases, stable emulsions are obtained which when cast and cured form goodcontinuous films.

EXAMPLE VIII The procedure of Example I is followed, except that thesolids content is similarly reduced to 40 percent of the unsaturatedaliphatic carboxylic acids are varied as follows:

a) 2 parts Fumaric Acid b) 2 parts Itaconic Acid c) 2 parts Fumaric Acid2 parts ltaconic Acid (reducing styrene by 2 parts) d) 3 parts ItaconicAcid 2 parts Methacrylic Acid (reducing styrene by 3 parts) e) 6 partsAcrylic Acid (reducing styrene by 4 parts) The novel copolymers of thepresent invention, either dried or in the form of the latices in whichthey are obtained, are suitable for a wide variety of uses in the art.They are unusually stable to intense mechanical shear, freeze-thawcycling and the addition of electrolytes such as mineral acids,polyvalent metal salts and the like. They can be compounded with a widevariety of additives such as pigments, clays, salts, protectivecolloids, wetting agents, plasticizers, resins, waxes, etc., in order toobtain a wide range of products for use in all fields in which emulsionpolymers are now used. They are compatible with many other commerciallatices and tolerate pigment and filler loading. They can be used in awide variety of adhesive applications particularly for laminatingtogether similar or dissimilar materials, such as for bonding syntheticplastics to fabrics of natural or synthetic origin in the application ofpolyurethane to fabrics, and other adhesive sizing and coatingapplications, and particularly with paper, leather and textiles. Thesenovel latices, either alone or compounded with other resins, or latices,form films which set up rapidly and adhere well to a number of polar andnon-polar surfaces. In wet bonding of porous surfaces, penetration isuniform so that film thickness on the surface can be readily met bycompounding with plasticizers, borates, solvents, pigments, andthickeners or other modifying resins or latices. Among the types ofsurfaces on which they can be used, either as coatings or as adhesivesbetween two similar or dissimilar surfaces are paper, glass, natural andsynthetic fibers, wood, aluminum foil, steel, leather and the like. Inpaper applications, these novel latices are useful as a pigment binderfor Georgia clay, TiO and CaCO Where applied to porous materials theyimpart improved oil and grease resistance, light stability, improveddye-ability and printing and have good adhesion to paper and a varietyof natural and synthetic fabrics. The films from these novel laticeshave good affinity for vat, sulfur, acid, disperse and direct dyes andtheir application as a surface coating or sizing to a variety offabrics, particularly synthetic fabrics and films, improves thedyeability thereof and imparts antistatic properties. The films producedfrom the novel latices of the present invention can be applied and curedby heating (preferably from 120 to 205C) in order to effect crosslinking. Various curing aids can be used in this case, such asaminoplast resins, metal oxides, free radical sources including rubbervulcanizing agents and the like.

The novel latices of the present invention are also useful as opacifyingagents for liquid detergent compositions in amounts as low as from 1 to2 parts by weight of the latex per 100 parts of liquid detergentformulation.

The novel latices of the present invention have been found to becompatible with such commercial latices as those ofbutadiene-acrylonitrile latices, polyvinyl acetate copolymers,styrene-butadiene emulsions, vinyl acetate and vinyl stearatecopolymers, styrene emulsions, alkyd and acrylate emulsions or latices,and with such naturally occurring products as dextrin or starch. In thelatter application, the novel latices of the present invention may beused in starch or dextrin adhesive compositions. They are alsocompatible with other latices obtained by polymerization of vinylmonomers such as styree or acrylic esters with polyvinyl pyrrolidonesuch as those described in U.S. Pat. Nos. 3,244,657 and 3,244,658.

We wish it to be understood that we do not desire to be limited to theexact details shown and described, for obvious modifications will occurto a person skilled in the art.

Having thus described the invention, what we claim as new and desired tobe secured by Letters Patent, is as follows:

1. A graft copolymer ofa monomer mixture containing' at least onemonomeric unsaturated aliphatic carboxylic acid and at least one monomerselected from the group consisting of aliphatic conjugated dienes andmonoalkenyl aromatic compounds polymerized on a polymeric N-vinyl lactamsubstrate, said copolymer containing approximately by weight 0 to 98parts of said diene, 0 to parts of said monoalkenyl aromatic compound,0.5 to 20 parts of said acid, and l to 99 parts of said polymericlactam.

2. A graft copolymer as defined in claim 1 wherein said polymeric lactamis polymeric N-vinyl-2- pyrrolidone.

3. A graft copolymer as defined in claim 1 wherein said aliphaticconjugated diene is selected from the group consisting of 1,3-butadiene,2,3-methyl-l,3- butadiene, 2-methyl-l,3-butadiene and 2-chloro-l ,3-butadiene.

4. A graft copolymer as defined in claim 1 wherein said monoalkenylaromatic compound is styrene.

5. A graft copolymer as defined in claim 1 wherein said unsaturatedaliphatic carboxylic acid is selected from the group consisting ofacrylic-, methacrylic-, fumaricand itaconic acids.

6. A graft copolymer as defined in claim 1 wherein said aliphaticconjugated diene is selected from the group consisting of 1,3-butadiene,2-methyl-l ,3- butadiene and 2-chloro-l,3-butadiene, said monoalkenylaromatic compound is styrene, said unsaturated aliphatic carboxylic acidis selected from the group consisting of acrylic-, methacrylic-,fumaric-and itaconic acids and said polymeric lactam is polymericN-vinyl-2- pyrrolidone.

1. A GRAFT COPOLYMER OF A MONOMER MIXTURE CONTAINING AT LEAST ONEMONOMERIC UNSATURATED ALIPHATIC CARBOXYLIC ACID AND AT LEAST ONE MONOMERSELECTED FROM THE GROUP CONSISTING OF ALIPHATIC CONJUGATED DIENES ANDMONOALKENYL AROMATIC COMPOUNDS POLYMERIZED ON A POLYMERIC N-VINYL LACTAMSUBSTRATE, SAID COPOLYMER CONTANING APPROXIMATELY BY WEIGHT 0 TO 98PARTS OF SAID DIENE, 0 TO 75 PARTS OF SAID MONOALKENYL AROMATICCOMPOUND, 0.5 TO 20 PARTS OF SAID ACID, AND 1 TO 99 PARTS OF SAIDPOLYMERIC LACTAM.
 1. A graft copolymer of a monomer mixture containingat least one monomeric unsaturated aliphatic carboxylic acid and atleast one monomer selected from the group consisting of aliphaticconjugated dienes and monoalkenyl aromatic compounds polymerized on apolymeric N-vinyl lactam substrate, said copolymer containingapproximately by weight 0 to 98 parts of said diene, 0 to 75 parts ofsaid monoalkenyl aromatic compound, 0.5 to 20 parts of said acid, and 1to 99 parts of said polymeric lactam.
 2. A graft copolymer as defined inclaim 1 wherein said polymeric lactam is polymericN-vinyl-2-pyrrolidone.
 3. A graft copolymer as defined in claim 1wherein said aliphatic conjugated diene is selected from the groupconsisting of 1,3-butadiene, 2 -methyl-1,3-butadiene,2,3-dimethyl-1,3-butadiene and 2-chloro-1,3-butadiene.
 4. A graftcopolymer as defined in claim 1 wherein said monoalkenyl aromaticcompound is styrene.
 5. A graft copolymer as defined in claim 1 whereinsaid unsaturated aliphatic carboxylic acid is selected from the groupconsisting of acrylic-, methacrylic-, fumaric- and itaconic acids.